CN107556527A - A kind of composite nano carbon material powder and its manufacture method - Google Patents
A kind of composite nano carbon material powder and its manufacture method Download PDFInfo
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- CN107556527A CN107556527A CN201710842134.1A CN201710842134A CN107556527A CN 107556527 A CN107556527 A CN 107556527A CN 201710842134 A CN201710842134 A CN 201710842134A CN 107556527 A CN107556527 A CN 107556527A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of composite nano carbon material powder and its manufacture method, belong to rubber technical field, because carbon nanotube dust and graphene are formed carbon nano-tube solution and graphene solution by the manufacture method of the composite nano carbon material powder of the embodiment of the present invention respectively, reduce the agglomeration of CNT and graphene, then composite nano carbon material powder is manufactured by the way of carbon nano-tube solution and graphene solution high speed are to spray, realize graphene and CNT cross-mixing, the synergy of the CNT and graphene in composite nano carbon material can be given full play to, improve the tire containing a large amount of ground rubbers and regeneration carbon black of addition composite nano carbon material and the performance of rubber, realize largely using regeneration carbon black, the further improvement of the tire tread glue performance of ground rubber.
Description
This application claims Patent Office of the People's Republic of China, Application No. 201610853832.7, invention were submitted on 09 27th, 2016
The priority of the Chinese patent application of entitled " a kind of carbon nano ring protect rubber composite and preparation method thereof ", in its whole
Appearance is hereby incorporated by reference in the application.
Technical field
The present invention relates to rubber technical field, more particularly to a kind of composite nano carbon material powder and its manufacturer
Method.
Background technology
The whole world produces substantial amounts of junked tire per annual meeting, and ground rubber and regeneration carbon black are the main productions of junked tire processing
Thing, but carbon black reinforcing property is poor, due to ground rubber self-strength difference regeneration at present, cause they can not tire with
Widely applied in rubber.
To realize that ground rubber and regeneration carbon black are widely applied in tire and rubber in prior art, while also not
Reduce tire tread glue performance, avoid it is a large amount of using tire tread glue intensity can be caused significantly after regeneration carbon blacks, ground rubber under
Drop, generally selects and directly adds CNT and graphene respectively in conventional rubber formulations.Although CNT has excellent
Mechanical property, electric property and thermodynamic property;Heat conduction that graphene has also had, electric conductivity, still, directly in rubber
CNT and graphene are added in formula respectively, because CNT and graphene are nanometer materials, its own reunion
Phenomenon is very serious, heap density is very small, and it is difficult that the two is evenly mixed in into one to cause directly both are separately employed in material
Rise, the synergy of CNT and graphene can not be realized at all, also can not fully improve containing a large amount of ground rubbers and again
The tire of raw carbon black and the performance of rubber.
The content of the invention
The present invention provides a kind of composite nano carbon material powder and its manufacture method, it is intended to reduces CNT and graphite
The agglomeration of alkene, the synergy of CNT and graphene is given full play to, realize and CNT and graphene addition exist
It is used for the performance for improving tire and rubber in tire and rubber containing a large amount of ground rubbers and regeneration carbon black, realizes
It is a large amount of to use regeneration carbon black, the improvement of the tire tread glue intensity of ground rubber.
Concrete technical scheme provided by the invention is as follows:
In a first aspect, a kind of manufacture method of composite nano carbon material powder provided by the invention, the manufacture method
Including:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
The carbon nano-tube solution and the graphene solution are formed into graphene and carbon using high-pressure nozzle at a high speed to spray
The composite nano carbon material solution of nanometer composition;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
Optionally, it is described that carbon nanotube dust and dispersant are mixed with water conjunction, carbon nano-tube solution is prepared, is specially:
The carbon nanotube dust, the dispersant and the water are used 0.5~5:0.5~2:100 mass ratio phase
Mixing;
The mixed liquor of the carbon nanotube dust, the dispersant and the water is sonicated or high speed shear is divided
Dissipate, prepare the carbon nano-tube solution.
Optionally, it is described that graphene powder and dispersant are mixed with water conjunction, graphene solution is prepared, is specially:
The graphene powder, the dispersant and the water are used 0.25~5:0.5~2:100 mass ratio mutually mixes
Close;
The mixed liquor of the graphene powder powder, the dispersant and the water is sonicated or high speed shear is divided
Dissipate, prepare the graphene solution.
Optionally, it is described to use high-pressure nozzle at a high speed to spray, shape the carbon nano-tube solution and the graphene solution
Into graphene and the composite nano carbon material solution of carbon nanometer composition, it is specially:
The carbon nano-tube solution and the graphene solution is right using 150MPa~250MPa high-pressure nozzle high speed
Spray, the composite nano carbon material solution of graphene and carbon nanometer composition is formed, wherein, the flow of the high-pressure nozzle is 80L/
Hour~150L/ hours.
Second aspect, the embodiment of the present invention provide a kind of manufacture method of composite nano carbon material powder, the manufacture
Method includes:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
High speed shear is carried out to the carbon nano-tube solution, to reduce the flat of the CNT in the carbon nano-tube solution
Reunite radius, obtain carbon nano tube dispersion liquid;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
High speed shear is carried out to the graphene solution, to reduce the average aggregate of the graphene in the graphene solution
Radius, obtain graphene dispersing solution;
The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, form graphene and carbon nanometer composition
Composite nano carbon material solution;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
The third aspect, the embodiment of the present invention provide a kind of manufacture method of composite nano carbon material powder, the manufacture
Method includes:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
The carbon nano-tube solution is entered into vacuum lumen by the way of high pressure, uses diffusion in vacuum to reduce the carbon
The average aggregate radius of CNT in nanotube solution, obtains carbon nano tube dispersion liquid;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
The graphene solution is entered into vacuum lumen by the way of high pressure, uses diffusion in vacuum to reduce the graphite
The average aggregate radius of graphene in alkene solution, obtains graphene dispersing solution;
The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, form graphene and carbon nanometer composition
Composite nano carbon material solution;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
Optionally, it is described that carbon nanotube dust and dispersant are mixed with water conjunction, carbon nano-tube solution is prepared, is specially:
The carbon nanotube dust, the dispersant and the water are used 0.5~5:0.5~2:100 mass ratio phase
Mixing, prepares the carbon nano-tube solution.
Optionally, it is described that graphene powder and dispersant are mixed with water conjunction, graphene solution is prepared, is specially:
The graphene powder, the dispersant and the water are used 0.25~5:0.5~2:100 mass ratio mutually mixes
Close, prepare the graphene solution.
Fourth aspect, the embodiment of the present invention provide a kind of composite nano carbon material powder, the composite nano carbon materials
Feed powder body is manufactured using the manufacture method of above-mentioned any composite nano carbon material powder, and the composite nano carbon materials
The mass ratio of CNT and graphene is in feed powder body:1~100:1, the composite nano carbon material powder is at 3000 times
Graphene and CNT cross-mixing are presented under~30000 times of ESEMs.
5th aspect, the embodiment of the present invention provide a kind of composite nano carbon material powder, the composite nano carbon materials
The mass ratio of CNT and graphene is in feed powder body:1~100:1, the composite nano carbon material powder is at 3000 times
Graphene and CNT cross-mixing are presented under~30000 times of ESEMs, and the composite nano carbon material powder exists
" class sandwich structure " is presented under 3000 times~30000 times ESEMs.
Beneficial effects of the present invention are as follows:
The embodiment of the present invention provides a kind of manufacture method of composite nano carbon material powder, first by carbon nanotube dust
Conjunction is mixed with water with dispersant and prepares carbon nano-tube solution, and graphene powder and dispersant then are mixed with water into conjunction prepares graphite
Alkene solution;High-pressure nozzle is used to spray, to form graphene and carbon nanometer group at a high speed carbon nano-tube solution and graphene solution again
Into composite nano carbon material solution, obtained composite nano carbon finally spray-dried to composite nano carbon material solution
Material powder, due to the embodiment of the present invention composite nano carbon material powder manufacture method by carbon nanotube dust and graphite
Alkene forms carbon nano-tube solution and graphene solution respectively, the agglomeration of CNT and graphene is reduced, then using carbon
Nanotube solution and graphene solution manufacture composite nano carbon material powder to the mode of spray at a high speed, realize graphene and carbon
Nanotube cross-mixing, the synergy of the CNT and graphene in composite nano carbon material can be given full play to, is kept away
When exempting from directly by CNT and graphene addition in tire and rubber containing a large amount of ground rubbers and regeneration carbon black,
CNT and each self-forming cluster of graphene and can not act synergistically, improve addition composite nano carbon material and contain
The performance of the tire and rubber of a large amount of ground rubbers and regeneration carbon black, realize largely using regeneration carbon black, ground rubber
The further improvement of tire tread glue performance.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is a kind of schematic flow sheet of the manufacture method of composite nano carbon material powder of the embodiment of the present invention;
Fig. 2 be the embodiment of the present invention carbon nanotube dust under ESEM schematic diagram;
Fig. 3 be the embodiment of the present invention graphene powder under ESEM schematic diagram;
Fig. 4 is under the ESEM after being directly mutually mixed carbon nanotube dust and graphene powder in prior art
Schematic diagram;
Fig. 5 is schematic diagram under the ESEM of the composite nano carbon material powder of the embodiment of the present invention;
Fig. 6 is the schematic flow sheet of the manufacture method of another composite nano carbon material powder of the embodiment of the present invention;
Fig. 7 is the schematic flow sheet of the manufacture method of another composite nano carbon material powder of the embodiment of the present invention;
Fig. 8 is the structural representation that a kind of diamond of the embodiment of the present invention prepares scattered valve.
Embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, the present invention is made below in conjunction with accompanying drawing into
One step it is described in detail, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole implementation
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
All other embodiment, belongs to the scope of protection of the invention.
Term " comprising " and " having " and their any deformation in description and claims of this specification, meaning
Figure be to cover it is non-exclusive include, for example, containing the process of series of steps or unit, method, system, product or equipment
Be not necessarily limited to those steps or the unit clearly listed, but may include not list clearly or for these processes,
The intrinsic other steps of method, product or equipment or unit.
To reduce the agglomeration of CNT and graphene, the embodiment of the present invention provides a kind of composite nano carbon material
Powder and its manufacture method, carbon nanotube dust and dispersant are mixed with water conjunction first and prepare carbon nano-tube solution, then will
Graphene powder is mixed with water conjunction with dispersant and prepares graphene solution;Again by carbon nano-tube solution and graphene solution using high
Press shower nozzle at a high speed to spray, the composite nano carbon material solution of formation graphene and carbon nanometer composition, finally to composite nano
The spray-dried obtained composite nano carbon material powder of carbon material solution, due to the composite nano carbon materials of the embodiment of the present invention
Carbon nanotube dust and graphene are formed carbon nano-tube solution and graphene solution by the manufacture method of feed powder body respectively, reduce carbon
The agglomeration of nanotube and graphene, then manufactured by the way of carbon nano-tube solution and graphene solution high speed are to spray multiple
Mould assembly nano-carbon material powder, realizes graphene and CNT cross-mixing, can give full play to composite nano carbon materials
The synergy of CNT and graphene in material, avoid directly by CNT and graphene addition containing a large amount of regeneration
When in the tire and rubber of rubber powder and regeneration carbon black, CNT and each self-forming cluster of graphene and can not cooperate with
Effect, improve the tire for containing a large amount of ground rubbers and regenerating carbon black of addition composite nano carbon material and the property of rubber
Can, realize largely using regeneration carbon black, the further improvement of the tire tread glue performance of ground rubber.
Below in conjunction with Fig. 1~Fig. 7 to a kind of composite nano carbon material powder of the embodiment of the present invention and its manufacturer
Method is described in detail.
Embodiment one
With reference to shown in figure 1, a kind of manufacture method of the composite nano carbon material powder provided the embodiment of the present invention one
It is described in detail.With reference to shown in figure 1, a kind of manufacturer for composite nano carbon material powder that the embodiment of the present invention one provides
Method comprises the following steps:
Step 110:Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution.
The scanning electron microscopic picture of carbon nanotube dust with reference to shown in figure 2 can be seen that the group of carbon nanotube dust itself
Poly- phenomenon is very serious, as can be seen that itself agglomeration of carbon nanotube dust is very serious under 3000 times of ESEM.
Precisely in order to reduce itself agglomeration of carbon nanotube dust, the composite nano carbon material powder of the embodiment of the present invention one
Carbon nanotube dust and dispersant are mixed with water conjunction by manufacture method first, realize abundant expansion of the carbon nanotube dust in water
Dissipate, reduce itself agglomeration of carbon nanotube dust, while dispersant is also added in carbon nano-tube solution, can be further
Increase carbon nanotube dust to spread in water, fully reduce itself reuniting for carbon nanotube dust.
Wherein, it is preferred that the embodiment of the present invention one selects deionized water, and deionized water refers to eliminate miscellaneous in ionic species
Pure water after matter.Provided with reference to International Organization for standardization ISO/TC 147, " deionization " is defined as:" water is completely or incompletely
Remove ionic species." dispersant be it is a kind of intramolecular and meanwhile have two kinds of opposite natures of lipophile and hydrophily interface live
Property agent.The definition of dispersant is that dispersant can reduce solid or the material of liquid particle aggregation in dispersion.The work of dispersant
With being using the time required for wetting dispersing agent reduction completion dispersion process and energy, stablize the pigment dispersion disperseed,
Modified pigment particle surface properties, adjust the motility of pigment particles.Example, the dispersant of the embodiment of the present invention one can be
Polyvinylpyrrolidone (polyvinyl pyrrolidone, abbreviation PVP).
Specifically, carbon nanotube dust, dispersant and water are used 0.5~5:0.5~2:100 mass ratio mixes,
Use 0.5~5:0.5~2:Carbon nanotube dust, dispersant are mixed with water conjunction by the formula of 100 mass ratio, then again will
The mixed liquor of the carbon nanotube dust of the proportioning, dispersant and water is sonicated or high speed shear is disperseed, and prepares carbon nanometer
Pipe solution.Wherein, being ultrasonically treated can drive the mixed liquor of carbon nanotube dust, dispersant and water to resonate by ultrasonic wave, enter
And further agglomeration of the destroying carbon nanometer tube in carbon nano-tube solution;High speed shear typically uses high-speed shearing machine, shows
Example, with the linear velocity of the meter per second of 3000 revolutions per seconds~5000 revolutions per seconds of rotating speed and 10 meter per seconds~20 to carbon nanotube dust, point
The mixed liquor of powder and water is quickly stirred, and the shearing to carbon nano-tube solution is realized during stirring, to destroy carbon
Reunion of the nanotube in carbon nano-tube solution, increases carbon nanotube dust and is spread in water, further reduces CNT and exists
Agglomeration in carbon nano-tube solution.
Example, the embodiment of the present invention one can use carbon nanotube dust, dispersant and deionized water using 3:1:
100 mass ratio mixes, then again by the mixed liquor of the carbon nanotube dust of the proportioning, dispersant and deionized water 5000
Revolutions per second rotating speed and 15 meter per seconds linear velocity under carry out high speed shear disperse, prepare carbon nano-tube solution.
Example, carbon nanotube dust, dispersant and water can be used 4 by the embodiment of the present invention one:1.5:100 quality
It is then again that the mixed liquor of the carbon nanotube dust of the proportioning, dispersant and water is sonicated scattered than mixing, prepare carbon
Nanotube solution.
It should be noted that preferable, step 110, which is maintained under less than 5 DEG C of low temperature environment, to be implemented, namely step 110
During implementation, the temperature of carbon nano-tube solution remains at less than 5 DEG C, and carbon is configured in the low temperature environment below 5 DEG C
Nanotube solution, the molecular activity of carbon nanomaterial can be reduced, and then reduce the group of carbon nanomaterial in carbon nano-tube solution
Poly- radius.
Step 120:Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution.
The reunion that the scanning electron microscopic picture of graphene powder with reference to shown in figure 3 can be seen that graphene powder itself shows
As very serious, as can be seen that itself agglomeration of graphene powder is very serious under 900 times of ESEM.Exactly it is
Reduce itself agglomeration of graphene powder, the manufacture method of the composite nano carbon material powder of the embodiment of the present invention is first
Graphene powder and dispersant are first mixed with water conjunction, realize abundant diffusion of the graphene powder in water, reduces Graphene powder
Itself agglomeration of body, while dispersant is also added in graphene solution, graphene powder can be further increased in water
Middle diffusion, fully reduce itself reuniting for graphene powder.
Specifically, graphene powder, dispersant and water are used 0.25~5:0.5~2:100 mass ratio mixes, i.e.,
Using 0.25~5:0.5~2:Graphene powder, dispersant are mixed with water conjunction by the formula of 100 mass ratio, then again should
The mixed liquor of the graphene powder of proportioning, dispersant and water is sonicated or high speed shear is disperseed, and prepares graphene solution.
Wherein, being ultrasonically treated can drive the mixed liquor of graphene powder, dispersant and water to resonate by ultrasonic wave, and then further break
Agglomeration of the bad graphene in graphene solution;High speed shear typically uses high-speed shearing machine, example, with 3000 turns/
Second~linear velocity of the meter per second of 5000 revolutions per seconds of rotating speed and 10 meter per seconds~20 is to the mixed liquor of graphene powder, dispersant and water
Quickly stirred, the shearing to graphene solution is realized during stirring, to destroy graphene in graphene solution
Reunion, increase graphene powder and spread in water, further reduce agglomeration of the graphene in graphene solution.
It should be noted that preferable, the embodiment of the present invention one is from the deionized water in water as graphene solution
Volume, the degree of scatter of graphene can be improved using deionized water, reduce the presence of the other impurities in graphene solution.
Example, the embodiment of the present invention one can use graphene powder, dispersant and deionized water using 0.5:1:
100 mass ratio mixes, then again by the mixed liquor of the graphene powder of the proportioning, dispersant and deionized water 4000
Revolutions per second rotating speed and 15 meter per seconds linear velocity under carry out high speed shear disperse, prepare graphene solution.
Example, graphene powder, dispersant and water can be used 3 by the embodiment of the present invention one:1.5:100 mass ratio
Mix, it is then again that the mixed liquor of the graphene powder of the proportioning, dispersant and water is sonicated scattered, prepare graphene
Solution.
It should be noted that preferable, step 120, which is maintained under less than 5 DEG C of low temperature environment, to be implemented, namely step 120
During implementation, the temperature of graphene solution remains at less than 5 DEG C, and graphite is configured in the low temperature environment below 5 DEG C
Alkene solution, the molecular activity of graphene can be reduced, and then reduce the reunion radius of graphene in graphene solution.
Secondly it should be noted that the implementation procedure of step 110 and step 120, not sequencing, example, step
Rapid 110 can perform before step 120, can also perform again after step 120, can also be together with step 120 simultaneously
Perform, a pair of the embodiment of the present invention this do not limit.
Step 130:The carbon nano-tube solution and the graphene solution are formed into stone using high-pressure nozzle at a high speed to spray
The composite nano carbon material solution of black alkene and carbon nanometer composition.
Specifically, by the graphene solution prepared in the carbon nano-tube solution and step 120 that are prepared in step 110 using high
Shower nozzle is pressed mutually mixed under the impact of high-voltage high-speed to the carbon nano-tube solution after spray and graphene solution to spray at a high speed
Close, form the composite nano carbon material solution of graphene and carbon nanometer composition.Example, it will can prepare in step 110
Two height of the graphene solution prepared in carbon nano-tube solution and step 120 by a high-tension apparatus from mutually contradictory setting
Pressing high speed relative in shower nozzle, during to spray, impulsive force causes carbon nano-tube solution and graphene solution mutual to spray
Mixing and mutually blending, form the composite nano carbon material solution of graphene and carbon nanometer composition.
It should be noted that the graphene solution that will be prepared in the carbon nano-tube solution and step 120 that are prepared in step 110
During carrying out high speed to spray using high-pressure nozzle, the injection pressure of high-pressure nozzle can not be less than 150MPa, and be oppositely arranged
Two high-pressure nozzles spout between spacing can not be more than 60mm, if the injection pressure of high-pressure nozzle is too small, and relatively
Set two high-pressure nozzles spout between spacing set it is excessive when, it will cause from high-pressure nozzle spray carbon nanometer
The impulsive force of the contact site of pipe solution and graphene solution is too small, can not realize between carbon nano-tube solution and graphene solution
Be mutually mixed and mutually blend, namely CNT in composite nano carbon material solution and graphene can not be avoided each again
From cluster, it can not ensure that the CNT in composite nano carbon material solution and graphene fully blend and are interweaved.
Further, it is carbon nano-tube solution and graphene solution is right using 150MPa~250MPa high-pressure nozzle high speed
Spray, the composite nano carbon material solution of graphene and carbon nanometer composition is formed, wherein, the flow of high-pressure nozzle is 10L/ hours
~150L/ hours.
Example, the graphene solution prepared in the carbon nano-tube solution and step 120 that are prepared in step 110 can be adopted
It is that 200MPa high-pressure nozzles are carried out at a high speed to spray, after spray with 100 ls/h and 25 ls/h of flow respectively with pressure
Carbon nano-tube solution and graphene solution be mutually mixed under the impact of high-voltage high-speed, form graphene and carbon nanometer composition
Composite nano carbon material solution.
Example, the graphene solution prepared in the carbon nano-tube solution and step 120 that are prepared in step 110 can be adopted
It is that 150MPa high-pressure nozzles are carried out at a high speed to spray, after spray with 100 ls/h and 50 ls/h of flow respectively with pressure
Carbon nano-tube solution and graphene solution be mutually mixed under the impact of high-voltage high-speed, form graphene and carbon nanometer composition
Composite nano carbon material solution.
It should be noted that preferable, step 130 is molten to spray carbon nano-tube solution and graphene at a high speed using high-pressure nozzle
, it is necessary to remain that the temperature of carbon nano-tube solution and graphene solution, also can be at 5 DEG C below 5 DEG C during liquid
Implementation steps 130 under following low temperature environment.Example, it can use high-pressure nozzle at a high speed to spray carbon nano-tube solution and stone
During black alkene solution, lead to cooling water and realize the temperature for keeping carbon nano-tube solution and graphene solution below 5 DEG C.5
The molecule of carbon nano molecular and graphene molecules in low temperature environment below DEG C in carbon nano-tube solution and graphene solution is lived
Property is low, and molecular motion is slow, and then can reduce the agglomeration of carbon nanometer and graphene in composite nano carbon material solution.
Step 140:By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
Specifically, by the composite nano carbon material solution prepared in step 130 by the way of spray drying, remove multiple
Moisture in mould assembly nano-carbon material solution, when composite nano carbon material solution, in spray drying effect, to be issued to moisture content low
When 3%, that is, the composite nano carbon material of the embodiment of the present invention one is prepared.Wherein, the embodiment of the present invention one is answered
The mass ratio of CNT and graphene is in mould assembly nano-carbon material powder:1~100:1.
With reference to shown in figure 5, using the manufacture method of the composite nano carbon material powder of the embodiment of the present invention one, manufacture
Graphene and CNT cross-mixing is presented in composite nano carbon material powder under 3000 times~30000 times ESEMs,
And " class sandwich structure " is presented under 3000 times~30000 times ESEMs in the composite nano carbon material powder.Wherein,
" class sandwich structure " refers to that the composite nano carbon material powder of the embodiment of the present invention exists
Under 3000 times~30000 times ESEMs, hence it is evident that it is clipped in it can be seen that carrying out graphene powder among carbon nanopowder body,
Namely the composite nano carbon material powder of the embodiment of the present invention is under 3000 times~30000 times ESEMs, graphene powder
Together with carbon nanopowder body phase mutually blending, although it does not split boundary clearly, most of upper strata is presented on the whole
It is that most of graphene powder, lower floor is carbon nanopowder body for most of carbon nanopowder body, middle level, and graphene powder and carbon are received
Ground rice body can mutually be cooperateed with and played a role, and then can be improved addition composite nano carbon material and be contained a large amount of ground rubbers
With the tire of regeneration carbon black and the performance of rubber, realize largely using regeneration carbon black, the tire tread colloidality of ground rubber
The further improvement of energy.
Due to the embodiment of the present invention one composite nano carbon material powder manufacture method by carbon nanotube dust and stone
Black alkene forms carbon nano-tube solution and graphene solution respectively, reduces the agglomeration of CNT and graphene, then uses
Carbon nano-tube solution and graphene solution manufacture composite nano carbon material powder to the mode of spray at a high speed, realize graphene with
CNT cross-mixing, the synergy of the CNT and graphene in composite nano carbon material can be given full play to,
Avoid directly by CNT and graphene addition in tire and rubber containing a large amount of ground rubbers and regeneration carbon black
When, CNT and each self-forming cluster of graphene and can not act synergistically, improve addition composite nano carbon materials
Material containing a large amount of ground rubbers and regenerate the tire of carbon black and the performance of rubber, realize largely using regeneration carbon black, again
The further improvement of the tire tread glue performance of rubber powder.
Embodiment two
With reference to shown in figure 6, a kind of manufacture method of the composite nano carbon material powder provided the embodiment of the present invention two
It is described in detail.With reference to shown in figure 6, a kind of manufacturer for composite nano carbon material powder that the embodiment of the present invention two provides
Method comprises the following steps:
Step 210:Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution.
The scanning electron microscopic picture of carbon nanotube dust with reference to shown in figure 2 can be seen that the group of carbon nanotube dust itself
Poly- phenomenon is very serious, as can be seen that itself agglomeration of carbon nanotube dust is very serious under 3000 times of ESEM.
Precisely in order to reduce itself agglomeration of carbon nanotube dust, the composite nano carbon material powder of the embodiment of the present invention two
Carbon nanotube dust and dispersant are mixed with water conjunction by manufacture method first, realize abundant expansion of the carbon nanotube dust in water
Dissipate, reduce itself agglomeration of carbon nanotube dust, while dispersant is also added in carbon nano-tube solution, can be further
Increase carbon nanotube dust to spread in water, fully reduce itself reuniting for carbon nanotube dust.
Wherein, it is preferred that the embodiment of the present invention two selects deionized water, and deionized water refers to eliminate miscellaneous in ionic species
Pure water after matter.Provided with reference to International Organization for standardization ISO/TC 147, " deionization " is defined as:" water is completely or incompletely
Remove ionic species." dispersant be it is a kind of intramolecular and meanwhile have two kinds of opposite natures of lipophile and hydrophily interface live
Property agent.The definition of dispersant is that dispersant can reduce solid or the material of liquid particle aggregation in dispersion.The work of dispersant
With being using the time required for wetting dispersing agent reduction completion dispersion process and energy, stablize the pigment dispersion disperseed,
Modified pigment particle surface properties, adjust the motility of pigment particles.Example, the dispersant of the embodiment of the present invention can be poly-
Vinylpyrrolidone (polyvinyl pyrrolidone, abbreviation PVP).
Specifically, carbon nanotube dust, dispersant and water (or deionized water) are used 0.5~5:0.5~2:100
Mass ratio mixes, i.e., using 0.5~5:0.5~2:The formula of 100 mass ratio is by carbon nanotube dust, dispersant and aqueous phase
Mixing, prepare carbon nano-tube solution.
Example, the embodiment of the present invention two can use carbon nanotube dust, dispersant and deionized water using 3:1:
100 mass ratio mixes, and prepares carbon nano-tube solution.
Example, carbon nanotube dust, dispersant and water can be used 4 by the embodiment of the present invention two:1.5:100 quality
Than mixing, carbon nano-tube solution is prepared.
It should be noted that preferable, step 210, which is maintained under less than 5 DEG C of low temperature environment, to be implemented, namely step 210
During implementation, the temperature of carbon nano-tube solution remains at less than 5 DEG C, and carbon is configured in the low temperature environment below 5 DEG C
Nanotube solution, the molecular activity of carbon nanomaterial can be reduced, and then reduce the group of carbon nanomaterial in carbon nano-tube solution
Poly- radius.
Step 220:High speed shear is carried out to the carbon nano-tube solution, received with reducing the carbon in the carbon nano-tube solution
The average aggregate radius of mitron, obtains carbon nano tube dispersion liquid.
Disperse specifically, the carbon nano-tube solution prepared in step 210 is carried out into high speed shear using high-speed shearing machine, make
Standby carbon nano tube dispersion liquid, example, with the linear speed of the meter per second of 3000 revolutions per seconds~5000 revolutions per seconds of rotating speed and 10 meter per seconds~20
Spend and the mixed liquor of carbon nanotube dust, dispersant and water is quickly stirred, realized during stirring to CNT
The shearing of solution, with reunion of the destroying carbon nanometer tube in carbon nano-tube solution, reduce carbon nanomaterial in carbon nano-tube solution
Reunion radius, increase carbon nanotube dust and spread in water, further reduce group of the CNT in carbon nano-tube solution
Poly- phenomenon.
Preferably, during step 220 is maintained under less than 5 DEG C of low temperature environment and implemented, namely step 220 is implemented,
The temperature of carbon nano-tube solution remains at less than 5 DEG C, and the low temperature environment high speed shearing CNT below 5 DEG C is molten
Liquid, the molecular activity of carbon nanomaterial can be reduced, and then reduce the reunion radius of carbon nanomaterial in carbon nano-tube solution.
Step 230:Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution.
The reunion that the scanning electron microscopic picture of graphene powder with reference to shown in figure 3 can be seen that graphene powder itself shows
As very serious, as can be seen that itself agglomeration of graphene powder is very serious under 900 times of ESEM.Exactly it is
Reduce itself agglomeration of graphene powder, the manufacture method of the composite nano carbon material powder of the embodiment of the present invention two
Graphene powder and dispersant are mixed with water conjunction first, realize abundant diffusion of the graphene powder in water, reduces graphene
Itself agglomeration of powder, while dispersant is also added in graphene solution, it can further increase graphene powder and exist
Spread in water, fully reduce itself reuniting for graphene powder.
Specifically, graphene powder, dispersant and water (or deionized water) are used 0.25~5:0.5~2:100
Mass ratio mixes, and prepares graphene solution.It should be noted that preferable, the embodiment of the present invention selects deionized water conduct
The volume of graphene solution, the degree of scatter of graphene can be improved using deionized water, reduce other in graphene solution
The presence of impurity.
Example, the embodiment of the present invention two can use graphene powder, dispersant and deionized water using 0.5:1:
100 mass ratio mixes, and prepares graphene solution.
Example, graphene powder, dispersant and water can be used 3 by the embodiment of the present invention two:1.5:100 mass ratio
Mix, prepare graphene solution.
It should be noted that preferable, step 220, which is maintained under less than 5 DEG C of low temperature environment, to be implemented, namely step 220
During implementation, the temperature of graphene solution remains at less than 5 DEG C, and graphite is configured in the low temperature environment below 5 DEG C
Alkene solution, the molecular activity of graphene can be reduced, and then reduce the reunion radius of graphene in graphene solution.
Secondly it should be noted that the implementation procedure of step 210 and step 230, not sequencing, example, step
Rapid 210 can perform before step 230, can also be performed again after step 230, can also be together with step 230 simultaneously
Perform, the embodiment of the present invention two is not limited this.
Step 240:High speed shear is carried out to the graphene solution, to reduce the graphene in the graphene solution
Average aggregate radius, obtains graphene dispersing solution.
Disperse specifically, the graphene solution prepared in step 230 is carried out into high speed shear using high-speed shearing machine, prepare
Graphene dispersing solution, example, with the linear velocity pair of the meter per second of 3000 revolutions per seconds~5000 revolutions per seconds of rotating speed and 10 meter per seconds~20
The mixed liquor of graphene powder, dispersant and water is quickly stirred, and is realized during stirring and graphene solution is cut
Cut, to destroy reunion of the graphene in graphene solution, reduce the reunion radius of grapheme material in graphene solution, increase
Graphene powder spreads in water, further reduces agglomeration of the graphene in graphene solution.
Preferably, during step 240 is maintained under less than 5 DEG C of low temperature environment and implemented, namely step 240 is implemented,
The temperature of graphene solution remains at less than 5 DEG C, the low temperature environment high speed shearing graphene solution below 5 DEG C, can
To reduce the molecular activity of grapheme material, and then reduce the reunion radius of grapheme material in graphene solution.
Step 250:The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, graphene is formed and is received with carbon
Meter Zu Cheng composite nano carbon material solution.
Specifically, the graphene dispersion liquid phase that will be prepared in the carbon nano tube dispersion liquid and step 240 that are prepared in step 220
Mixing, it is prepared into the composite nano carbon material solution of CNT and graphene composition.It should be noted that step 250 exists
The graphene dispersing solution prepared in the carbon nano tube dispersion liquid and step 240 that are prepared in step 220 is mixed and is prepared into carbon and receives
, it is necessary to keep carbon nano tube dispersion liquid, graphene during the composite nano carbon material solution of mitron and graphene composition
Dispersion liquid and composite nano carbon material solution below 5 DEG C, also can in the low temperature environment below 5 DEG C implementation steps
250.Carbon nano molecular and graphene molecules in low temperature environment below 5 DEG C in carbon nano-tube solution and graphene solution
Molecular activity is low, and molecular motion is slow, and then can reduce the reunion of carbon nanometer and graphene in composite nano carbon material solution
Phenomenon.
Example, mass ratio can be used as 1~100:1 proportioning, the carbon nano tube dispersion liquid that will be prepared in step 220
The composite nano carbon materials for being prepared into CNT and graphene composition are mixed with the graphene dispersing solution prepared in step 240
Expect solution.
Step 260:By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
Specifically, step 260 is identical with above-mentioned steps 140, the implementation procedure of step 260 may be referred to above-mentioned steps
140, the embodiment of the present invention two is not repeated herein.
With reference to shown in figure 5, using the manufacture method of the composite nano carbon material powder of the embodiment of the present invention two, manufacture
Graphene and CNT cross-mixing is presented in composite nano carbon material powder under 3000 times~30000 times ESEMs,
And " class sandwich structure " is presented under 3000 times~30000 times ESEMs in the composite nano carbon material powder.Wherein,
" class sandwich structure " refers to the composite nano carbon material powder of the embodiment of the present invention in 3000 times~30000 times ESEMs
Under, hence it is evident that it is clipped in it can be seen that carrying out graphene powder among carbon nanopowder body, namely the composite nano carbon of the embodiment of the present invention
Material powder is under 3000 times~30000 times ESEMs, and graphene powder and carbon nanopowder body phase be mutually together with blending, although
It does not split boundary clearly, and still, it is that most of carbon nanopowder body, middle level is graphene that most of upper strata is presented on the whole
Most of powder, lower floor is carbon nanopowder body, and graphene powder and carbon nanopowder body can mutually be cooperateed with and played a role, and then
The tire containing a large amount of ground rubbers and regeneration carbon black of addition composite nano carbon material and the property of rubber can be improved
Can, realize largely using regeneration carbon black, the further improvement of the tire tread glue performance of ground rubber.
Due to the embodiment of the present invention two composite nano carbon material powder manufacture method by carbon nanotube dust and stone
Black alkene forms carbon nano-tube solution and graphene solution respectively, reduces the agglomeration of CNT and graphene, then uses
The mode of high speed shear distinguishes carbon nano-tube solution and graphene solution further disperses, and obtains carbon nano dispersion fluid and graphene
Dispersion liquid, the reunion radius of carbon nanomaterial in carbon nano-tube solution is further reduced, increases carbon nanotube dust in water
Middle diffusion, carbon nano dispersion fluid and graphene dispersing solution are then mutually mixed manufacture composite nano carbon according to certain ratio
Material powder, graphene and CNT cross-mixing are realized, the carbon that can be given full play in composite nano carbon material is received
The synergy of mitron and graphene, avoid directly by CNT and graphene addition containing a large amount of ground rubbers and regeneration
When in the tire and rubber of carbon black, CNT and each self-forming cluster of graphene and can not act synergistically, improve
The tire containing a large amount of ground rubbers and regeneration carbon black of addition composite nano carbon material and the performance of rubber are improved, it is real
It is now a large amount of to use regeneration carbon black, the further improvement of the tire tread glue performance of ground rubber.
Embodiment three
With reference to shown in figure 7, a kind of manufacture method of the composite nano carbon material powder provided the embodiment of the present invention three
It is described in detail.With reference to shown in figure 7, a kind of manufacturer for composite nano carbon material powder that the embodiment of the present invention three provides
Method comprises the following steps:
Step 310:Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution.
Specifically, step 310 is identical with above-mentioned steps 210, the implementation procedure of step 310 may be referred to above-mentioned steps
210, the embodiment of the present invention three is not repeated herein.
Step 320:The carbon nano-tube solution is entered into vacuum lumen by the way of high pressure, uses diffusion in vacuum to subtract
The average aggregate radius of CNT in the small carbon nano-tube solution, obtains carbon nano tube dispersion liquid.
Specifically, by tight diamond prepared by carbon nano-tube solution into scattered valve, and bear hyperpressure energy
Three kinds of shearing, hole, collision average dispersion effects caused by abrupt release in slit, while carbon nano-tube solution needs
Under the cooling of low temperature water-bath, less than 5 DEG C of low temperature is maintained at, ensures the CNT for entering vacuum lumen by the way of high pressure
Carbon nano-tube solution even of the solution after diffusion in vacuum and it is not easy to re-form agglomeration, is easy to CNT
It is scattered in carbon nano-tube solution.
Example, with reference to shown in figure 8, carbon nano-tube solution 1 is entered in vacuum chamber 4 by the central through hole of valve chamber 2, its
In, central through hole of the carbon nano-tube solution 1 through valve chamber 2 enter vacuum chamber 4 during, it is necessary to bear the shearing of shearing ring 3, valve
Caused cavitation in the collision of core 5 and vacuum chamber 4, realize carbon nano-tube solution even and be not easy the group of re-forming
Poly- phenomenon, it is easy to CNT scattered in carbon nano-tube solution, obtains the carbon nano tube dispersion liquid of even.
Step 330:Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution.
Specifically, step 330 is identical with above-mentioned steps 230, the implementation procedure of step 330 may be referred to above-mentioned steps
230, the embodiment of the present invention three is not repeated herein.
Step 340:The graphene solution is entered into vacuum lumen by the way of high pressure, uses diffusion in vacuum to reduce
The average aggregate radius of graphene in the graphene solution, obtains graphene dispersing solution.
Specifically, by tight diamond prepared by graphene solution into scattered valve, and bear hyperpressure energy and exist
Three kinds of shearing, hole, collision average dispersion effects caused by abrupt release in slit, while graphene solution is needed in low temperature
Under the cooling of water-bath, less than 5 DEG C of low temperature is maintained at, ensures that the graphene solution into vacuum lumen by the way of high pressure passes through
Graphene solution even after diffusion in vacuum and it is not easy to re-form agglomeration, is easy to graphene molten in graphene
It is scattered in liquid.
It should be noted that graphene solution is entered into vacuum lumen by the way of high pressure in step 340, using vacuum
Diffusion may be referred to carbon in step 320 with reducing the implementation process of the average aggregate radius of the graphene in graphene solution
Nanotube solution enters vacuum lumen by the way of high pressure, uses diffusion in vacuum to reduce the carbon nanometer in carbon nano-tube solution
The implementation process of the average aggregate radius of pipe, the embodiment of the present invention three are not repeated herein.
Step 350:The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, graphene is formed and is received with carbon
Meter Zu Cheng composite nano carbon material solution.
Specifically, step 360 is identical with above-mentioned steps 260, the implementation procedure of step 360 may be referred to above-mentioned steps
260, the embodiment of the present invention three is not repeated herein.
Step 360:By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
Specifically, step 350 is identical with above-mentioned steps 250, the implementation procedure of step 350 may be referred to above-mentioned steps
250, the embodiment of the present invention three is not repeated herein.
Due to the embodiment of the present invention two composite nano carbon material powder manufacture method by carbon nanotube dust and stone
Black alkene forms carbon nano-tube solution and graphene solution respectively, reduces the agglomeration of CNT and graphene, then uses
Three kinds of shearing of diffusion in vacuum, hole, collision average dispersion effects are further to carbon nano-tube solution and graphene solution respectively
It is scattered, carbon nano dispersion fluid and graphene dispersing solution are obtained, further reduces the group of carbon nanomaterial in carbon nano-tube solution
Poly- radius, increase carbon nanotube dust and spread in water, then by carbon nano dispersion fluid and graphene dispersing solution according to certain
Ratio be mutually mixed manufacture composite nano carbon material powder, realize graphene and CNT cross-mixing, Ke Yichong
The synergy of the CNT and graphene in composite nano carbon material is waved in distribution, is avoided CNT and graphite directly
When alkene addition is in tire and rubber containing a large amount of ground rubbers and regeneration carbon black, CNT and each idiomorphism of graphene
Into cluster without that can act synergistically, improve addition composite nano carbon material contains a large amount of ground rubbers and regenerated carbon
Black tire and the performance of rubber, realize and largely enter one using the tire tread glue performance of regeneration carbon blacks, ground rubber
Step improves.
Below in conjunction with specific application examples, compound the receiving of CNT and graphene composition to the embodiment of the present invention
Rice carbon material powder is used for technique effect during performance in the tire and rubber containing a large amount of ground rubbers and regeneration carbon black
Carry out detailed comparisons' explanation.
Table one
Title material | Rubber one | Rubber two | Rubber three | Rubber four | Rubber five |
Rubber | 100 | 100 | 100 | 100 | 100 |
Zinc oxide | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
Stearic acid | 1 | 1 | 1 | 1 | 1 |
Age resistor | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
Sulphur | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
Accelerator | 1 | 1 | 1 | 1 | 1 |
Regenerate carbon black | 50 | 50 | 50 | 50 | 50 |
Ground rubber | 30 | 30 | 30 | 30 | 30 |
CNT | 5 | 4 | |||
Graphene | 5 | 1 | |||
Composite nano carbon material | 5 | ||||
Material amounts to | 188.5 | 193.5 | 193.5 | 193.5 | 193.5 |
Hardness (°) | 55 | 63 | 63 | 63 | 63 |
Stretch (MPa) | 16.64 | 17.78 | 20.68 | 21.77 | 24.83 |
Elongation (%) | 727 | 453 | 578.25 | 527 | 595 |
Tearing strength (KN/m) | 62.39 | 79.52 | 105.74 | 108.93 | 137.54 |
DIN(cm3) | 0.1648 | 0.1594 | 0.1547 | 0.1428 | 0.1157 |
80 DEG C of thermal conductivity factors (W/mK) | 0.168 | 0.227 | 0.242 | 0.249 | 0.284 |
From the comparative analysis of table one, it can be seen that the formula of rubber two with the addition of graphene, rubber relative to rubber one
Three formula with the addition of CNT relative to rubber one, and the formula of rubber four with the addition of CNT and stone relative to rubber one
Carbon nanomaterial (CNT and/or graphene) is with the addition of in black alkene, the i.e. formula of rubber two, rubber three and rubber four,
Although it can be made up using high reinforcement, high abrasion and the high thermal conductivity of carbon nanomaterial in the formula of rubber one due to a large amount of
Addition regeneration carbon black and ground rubber caused by stretching, tearing strength it is poor, it is wear-resisting it is poor, ageing properties are poor, heat conduction and heat radiation poor performance
The defects of so that the rubber compounding of a large amount of addition regeneration carbon blacks and ground rubber has reached the performance of normal rubber compounding.
As can be seen from Table I, rubber four is after normal temperature physical property, aging in intensity and tear, anti-wear performance and heat conductivility
Rubber two and rubber three are superior to, temperature rises also superior to rubber two and rubber three in terms of compression heat generation.Its main cause is
CNT and graphene are with the addition of simultaneously in the formula of rubber four, because CNT and graphene are during rubber processing
Obtained slight dispersion mixing, CNT and graphene have on microcosmic it is slight interspersed, although being still aggregating state,
But it also form slight synergy.
Rubber five in table one and rubber one, rubber two, rubber three, rubber four are compared it can be found that due to rubber
The composite nano carbon material of the embodiment of the present invention is with the addition of in five formula, in the case where keeping other stable performances, its
Tensile property, tearing strength, thermal conductivity factor etc. have obtained larger lifting, and analysis is the reason is that rubber five employs this
The composite nano carbon material of invention, due to the CNT and the complete phase of graphene in the composite nano carbon material of the present invention
It is mutually interspersed, and the CNT in the composite nano carbon material of the present invention and graphene are no longer aggregating states, carbon nanometer
Manage and fully played with the mutual synergy of graphene, therefore the carbon in the composite nano carbon material of the present invention is received
Mitron there is a greater chance that contact rubber, realizes the more preferable combination of carbon nanomaterial and rubber, therefore the present invention with graphene
Composite nano carbon material realize rubber five and have bigger lifting relative to rubber four in the performance such as reinforcement, wear-resisting.
The CNT being additionally, since in the composite nano carbon material of the present invention is mutually put up a bridge with graphene, and conduction is led
Heat passage is opened completely, therefore uses the rubber five of the composite nano carbon material of the present invention relative to rubber one, rubber two, rubber
Glue three, rubber four, its heat conduction and heat radiation ability have obtained significantly being lifted.Furthermore due to the composite nano carbon of the present invention
The agglomeration of CNT and graphene in material there's almost no, and CNT becomes more with graphene in rubber
It is submissive, therefore heat also becomes lower, with reference to the characteristics of the low-heat-generation of regeneration carbon black and ground rubber so that rubber five is obtaining
Target that is high performance while also realizing low-heat-generation and high heat conduction.
By adding the rubber five for the composite nano carbon material that the embodiment of the present invention manufactures in table one and adding stone simultaneously
The comparative analysis of the performance parameter of the rubber four of black alkene and CNT can be seen that directly adds carbon nanometer in rubber compounding
Pipe and graphene, can not be acted synergistically, although rubber well due to CNT and each self-forming cluster of graphene
Four relative to the rubber one for not adding CNT and graphene, can improve to a certain extent containing a large amount of ground rubbers and again
The tire of raw carbon black and the performance of rubber, still, relative to the composite nano carbon materials of addition manufacture of the embodiment of the present invention
The rubber five of material, its for the tire containing a large amount of ground rubbers and regeneration carbon black and the tensile property of rubber, elongation,
The lifting effect of tearing strength, 130 DEG C of thermal conductivity factors, 130 DEG C of thermal diffusion coefficients etc., hence it is evident that not as adding embodiment of the present invention system
The lifting effect of the rubber five for the composite nano carbon material made.
Obviously, those skilled in the art can carry out various changes and modification without departing from this hair to the embodiment of the present invention
The spirit and scope of bright embodiment.So, if these modifications and variations of the embodiment of the present invention belong to the claims in the present invention
And its within the scope of equivalent technologies, then the present invention is also intended to comprising including these changes and modification.
Claims (10)
1. a kind of manufacture method of composite nano carbon material powder, it is characterised in that the manufacture method includes:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
The carbon nano-tube solution and the graphene solution are formed into graphene and carbon nanometer using high-pressure nozzle at a high speed to spray
The composite nano carbon material solution of composition;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
2. manufacture method according to claim 1, it is characterised in that described by carbon nanotube dust and dispersant and aqueous phase
Mixing, carbon nano-tube solution is prepared, be specially:
The carbon nanotube dust, the dispersant and the water are used 0.5 ~ 5:0.5~2:100 mass ratio mixes;
The mixed liquor of the carbon nanotube dust, the dispersant and the water is sonicated or high speed shear is disperseed, system
The standby carbon nano-tube solution.
3. manufacture method according to claim 1, it is characterised in that described to be mixed with water graphene powder and dispersant
Close, prepare graphene solution, be specially:
The graphene powder, the dispersant and the water are used 0.25 ~ 5:0.5~2:100 mass ratio mixes;
The mixed liquor of the graphene powder powder, the dispersant and the water is sonicated or high speed shear is disperseed,
Prepare the graphene solution.
4. manufacture method according to claim 1, it is characterised in that described by the carbon nano-tube solution and the graphite
Alkene solution, at a high speed to spraying, forms the composite nano carbon material solution of graphene and carbon nanometer composition, specifically using high-pressure nozzle
For:
By the carbon nano-tube solution and the graphene solution using 150MPa ~ 250MPa high-pressure nozzle at a high speed to spray, shape
Into graphene and the composite nano carbon material solution of carbon nanometer composition, wherein, the flow of the high-pressure nozzle for 80L/ hours ~
150L/ hours.
5. a kind of manufacture method of composite nano carbon material powder, it is characterised in that the manufacture method includes:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
High speed shear is carried out to the carbon nano-tube solution, to reduce the average group of the CNT in the carbon nano-tube solution
Poly- radius, obtains carbon nano tube dispersion liquid;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
High speed shear is carried out to the graphene solution, to reduce the average aggregate of the graphene in the graphene solution half
Footpath, obtain graphene dispersing solution;
The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, formation graphene forms compound with carbon nanometer
Type nano-carbon material solution;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
6. a kind of manufacture method of composite nano carbon material powder, it is characterised in that the manufacture method includes:
Carbon nanotube dust and dispersant are mixed with water conjunction, prepare carbon nano-tube solution;
The carbon nano-tube solution is entered into vacuum lumen by the way of high pressure, uses diffusion in vacuum to reduce the carbon nanometer
The average aggregate radius of CNT in pipe solution, obtains carbon nano tube dispersion liquid;
Graphene powder and dispersant are mixed with water conjunction, prepare graphene solution;
The graphene solution is entered into vacuum lumen by the way of high pressure, it is molten to reduce the graphene to use diffusion in vacuum
The average aggregate radius of graphene in liquid, obtains graphene dispersing solution;
The carbon nano tube dispersion liquid and the graphene dispersing solution are mixed, formation graphene forms compound with carbon nanometer
Type nano-carbon material solution;
By the spray-dried obtained composite nano carbon material powder of the composite nano carbon material solution.
7. the manufacture method according to claim 5 or 6, it is characterised in that it is described by carbon nanotube dust and dispersant and
Aqueous phase mixes, and prepares carbon nano-tube solution, is specially:
The carbon nanotube dust, the dispersant and the water are used 0.5 ~ 5:0.5~2:100 mass ratio mixes, system
The standby carbon nano-tube solution.
8. the manufacture method according to claim 5 or 6, it is characterised in that described by graphene powder and dispersant and water
Mix, prepare graphene solution, be specially:
The graphene powder, the dispersant and the water are used 0.25 ~ 5:0.5~2:100 mass ratio mixes, system
The standby graphene solution.
9. a kind of composite nano carbon material powder, it is characterised in that the composite nano carbon material powder uses such as right
It is required that the manufacture method manufacture of the composite nano carbon material powder described in 1 ~ 8 any one, and the composite nano carbon material
The mass ratio of CNT and graphene is in powder:1~100:1, the composite nano carbon material powder 3000 times ~
Graphene and CNT cross-mixing are presented under 30000 times of ESEMs.
A kind of 10. composite nano carbon material powder, it is characterised in that CNT in the composite nano carbon material powder
Mass ratio with graphene is:1~100:1, the composite nano carbon material powder is under 3000 times ~ 30000 times ESEMs
Graphene and CNT cross-mixing is presented, and the composite nano carbon material powder is in 3000 times ~ 30000 times scanning electricity
" class sandwich structure " is presented under mirror.
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CN107556527B (en) | 2019-03-12 |
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